Advance in wet chemistry enables the sophisticated design of nanocrystal quantum dots (QDs) and allows unprecedented color purity and brightness, promising their useful applications in a variety of light-emitting applications. A representative example is core/shell heterostructures, in which charge carriers are effectively decoupled from structural artifacts to generate photons efficiently. Despite the development of widely accepted synthetic protocols for Cd- or Pb-based QDs, the progress in heterostructuring environmentally benign QDs has been lagging behind, and so is the practical use of these QDs. Herein, we present a design principle for InP/ZnSe x S1–x heterostructured QDs. A principal design approach is the growth of uniformly thick inorganic shell consisting of a ZnSe x S1–x inner shell and a ZnS outermost shell that effectively confines electrons from spreading inward of QDs. Comprehensive studies across synthesis, spectroscopic analysis, and calculation uncover that the presence of Se near the InP emissive core enables a uniform shell growth to an extended thickness and the S-rich exterior shell ensures the decoupling of the electron wave function from the surface trap states. Engineering composition profile across multiple shells enables us to realize InP/thick-shell QDs meeting the requirements of light-emitting applications such as high photoluminescence quantum yield, narrow spectral bandwidth, and enhanced photochemical robustness. We capitalize on bright, robust, and color-pure InP/ZnSe x S1–x /ZnS QDs with a range of emission wavelength covering from cyan to red regions by exemplifying their use in the primary-color light-emitting diodes (peak external quantum efficiency of 3.78 and 3.92% for green- and red-emitting ones, respectively).

To capitalize on shape- and structure-dependent properties of semiconductor nanorods (NRs), high-precision control and exquisite design of their growth are desired. Cadmium chalcogenide (CdE; E = S or Se) NRs are the most studied class of such, whose growth exhibits axial anisotropy, i.e., different growth rates along the opposite directions of {0001} planes. However, the mechanism behind asymmetric axial growth of NRs remains unclear because of the difficulty in instant analysis of growth surfaces. Here, we design colloidal dual-diameter semiconductor NRs (DDNRs) under the quantum confinement regime, which have two sections along the long axis with different diameters. The segmentation of the DDNRs allows rigorous assessment of the kinetics of NR growth at a molecular level. The reactivity of a terminal facet passivated by an organic ligand is governed by monomer diffusivity through the surface ligand monolayer. Therefore, the growth rate in two polar directions can be finely tuned by controlling the strength of ligand-ligand attraction at end surfaces. Building on these findings, we report the synthesis of single-diameter CdSe/CdS core/shell NRs with CdSe cores of controllable position, which reveals a strong structure-optical polarization relationship. The understanding of the NR growth mechanism with controllable anisotropy will serve as a cornerstone for the exquisite design of more complex anisotropic nanostructures.

Many heterogeneous catalytic reactions occur at high temperatures, which may cause large energy costs, poor safety, and thermal degradation of catalysts. Here, we propose a light-assisted surface reaction, which catalyze the surface reaction using both light and heat as an energy source. Conventional metal catalysts such as ruthenium, rhodium, platinum, nickel, and copper were tested for CO2 hydrogenation, and ruthenium showed the most distinct change upon light irradiation. CO2 was strongly adsorbed onto ruthenium surface, forming hybrid orbitals. The band gap energy was reduced significantly upon hybridization, enhancing CO2 dissociation. The light-assisted CO2 hydrogenation used only 37% of the total energy with which the CO2 hydrogenation occurred using only thermal energy. The CO2 conversion could be turned on and off completely with a response time of only 3 min, whereas conventional thermal reaction required hours. These unique features can be potentially used for on-demand fuel production with minimal energy input.

Colloidal semiconductor nanocrystals hold great promise in display technologies, as the tunable energy levels and narrow emission bandwidth allow for wide gamut in color space. Impetus for energy-efficient, high-color-quality display has driven the surge of interest in electrically driven quantum dot-based lightemitting diodes (QD-LEDs). While extensive efforts have led to synthesis of QDs with near-unity photoluminescence quantum yield and fabrication of QD-LEDs with external quantum efficiency reaching to the theoretical limit (∼20%), low out-coupling factor poses a challenge in the way of improving the device performance when spherical QDs are used. Geometrically anisotropic nanocrystals (NCs) such as nanorods or nanoplatelets represent a unique possible solution to enhancing light extraction efficiency. In this Perspective, we highlight important design principles of individual anisotropic NCs and their assembly in the context of LED applications.

We developed a new chemical strategy to enhance the stability of lead selenide nanocrystals (PbSe NCs) against oxidation through the surface passivation by P-O- moieties. In the synthesis of PbSe NCs, tris(diethylamino)phosphine (TDP) selenide (Se) was used as a Se precursor, and the resulting PbSe NCs withstood long-term air exposure while showing nearly no sign of oxidation. Nuclear magnetic resonance (NMR) spectroscopy reveals that TDP derivatives passivate the surface of PbSe NC. Through a series of ligand cleavage reactions, we found that the TDP derivatives are bound on NC surface through the P-O- moiety. Based on such understanding, it turned out that direct addition of various PAs during the synthesis of PbSe NCs also results in the NCs whose absorption spectrum remains nearly intact after air exposure for weeks. The P-O- moieties render the NCs stable in the operation of field effect transistors, suggesting that our findings can enable the use of air stable PbSe NCs in wider array of optoelectronic applications.

We report synthesis of PbSe nanorods (NRs) and PbSe/ CdSe axial heterojunction NRs via direct Cd-to-Pb cation exchange in CdSe NRs. Use of suited ligand−cation combinations enables the cation exchange while keeping the nanomaterial morphology intact. For example, solvation of Cd 2+ using oleylamine (OLA) allows for the cation exchange process, which would not be possible by using oleic acid instead of OLA. A mild cation exchange process, such as mixing Pb-oleate and OLA with CdSe NRs at 130 or 150°C, results in anisotropic replacement of CdSe into PbSe along the ⟨0001⟩ direction of wurtzite CdSe, and a partial conversion leads to the formation of heterostructure NRs containing axial CdSe/PbSe heterojunctions. While the cation exchange proceeds at both tips of CdSe NRs, exchange appears to be faster on (0001̅ ) planes. Binding energy calculation based on density functional theory reveals that OLA binds strongly to the (0001̅ ) facet of CdSe NRs, leading to asymmetric cation exchange. This protocol to convert CdSe nanocrystals directly into PbSe broadens the design range of CdSe/PbSe heterojunction nanomaterials potentially with various morphologies because template CdSe nanocrystals can be prepared in different shapes via colloidal synthesis.

Growth of monodisperse indium phosphide (InP) quantum dots (QDs) represents a pressing demand in display applications, as size uniformity is related to color purity in display products. Here, we report the colloidal synthesis of InP QDs in the presence of Zn precursors in which size uniformity is markedly enhanced as compared to the case of InP QDs synthesized without Zn precursors. Nuclear magnetic resonance spectroscopy, X-ray photoelectron spectroscopy, and mass spectrometry analyses on aliquots taken during the synthesis allow us to monitor the appearance of metal− phosphorus complex intermediates in the growth of InP QDs. In the presence of zinc carboxylate, intermediate species containing Zn−P bonding appears. The Zn−P intermediate complex with P(SiMe 3 ) 3 exhibits lower reactivity than that of the In−P complex, which is corroborated by our prediction based on density functional theory and electrostatic potential charge analysis. The formation of a stable Zn−P intermediate complex results in lower reactivity, which enables slow growth of QDs and lowers the extreme reactivity of P(SiMe 3 ) 3 , hence monodisperse QDs. Insights from experimental and theoretical studies advance mechanistic understanding and control of nucleation and growth of InP QDs, which are key to the preparation of monodisperse InP-based QDs in meeting the demand of the display market.

In this study, we report the shape dependence of fluorescence polarization from colloidal CdSe nanoplatelets (NPLs). Despite the symmetry of their cubic unit cell structure, CdSe nanocrystals grow into two-dimensional platelets in the presence of acetate precursors, and the resulting NPLs exhibit polarized emission. The amount of acetate salts introduced during the synthesis plays a critical role in controlling the lateral aspect ratio of CdSe NPLs. Specifically, the more the acetate hydrate presents, the more squarelike face of NPLs emerges. As a result, we achieved CdSe NPLs with varying lateral aspect ratios ranging from 1.1 to 4.5 in our experimental conditions. At the same thickness, CdSe NPLs with higher lateral aspect ratios exhibit higher fluorescence polarization. We analyzed the shape dependence by preparing films of CdSe NPLs dropcast under an electric field and measuring emission and absorption polarizations from CdSe NPL films of known orientation parameters. The emission polarization stays nearly unchanged regardless of shape anisotropy of CdSe NPLs, while the absorption polarization is affected by the lateral aspect ratio. Now that these results allude to a likelihood that absorption polarization is responsible for the shape dependence of fluorescence polarization, we design a model to assess the correlation between the geometry of NPLs and the optical transition polarization by way of the local field effect. Theoretically estimated absorption polarization also shows shape dependence similar to experimental data, which suggests that the anisotropic local field effect is a primary denominator of shape-dependent fluorescence polarization in CdSe NPLs.